Azomethine pigments

ABSTRACT

Azomethine pigments of the formula  AND METAL COMPLEXES THEREOF, WHEREIN A denotes an isocyclic or heterocyclic aromatic radical, R denotes a H atom, an alkyl group containing 1-6 C atoms, or an aryl radical, X2 and X4  denote H atoms or halogen atoms, X1 and X3 denote H atoms or halogen atoms, alkoxy or alkylmercapto groups containing 1-6 C atoms, cycloalkoxy groups containing 5-6 C atoms, or aralkoxy, aryloxy or arylmercapto groups, it being possible for one of the substituents X1-X4 also to be a nitro group which are useful for pigmenting of high molecular material.

It has been found that new, valuable azomethine pigments of the formula ##SPC2##

Wherein A denotes an isocyclic or heterocyclic aromatic radical, R denotes a H atom, an alkyl group containing 1-6 C atoms, or an aryl radical, X₂ and X₄ denote H atoms or halogen atoms, X₁ and X₃ denote H atoms or halogen atoms, alkoxy or alkylmercapto groups containing 1-6 C atoms, cycloalkoxy groups containing 5-6 C atoms, or aralkoxy, aryloxy or arylmercapto groups, it being possible for one of the substituents X₁ -X₄ also to be a nitro group, are obtained if

A. AN ISOINDOLINONE HYDRAZONE OF THE FORMULA ##SPC3##

Particularly an isoindolinone hydrazone of the formula ##SPC4##

Wherein X₅ and X₇ denote H atoms or chlorine atoms or alkoxy groups containing 1-4 C atoms, X₆ and X₈ denote H atoms or chlorine atoms, X₆ and X₈ representing chlorine atoms if X₅ and X₇ denote alkoxy groups, is condensed with a compound of the formula ##STR1## wherein Q denotes an O atom or an imino group, or

B. AN ISOINDOLINONE OF THE FORMULA ##SPC5##

Wherein V denotes a group of the formula ##STR2## wherein Z₁ denotes an imino or thio group and the Z₂ 's denote halogen atoms, or alkoxy or secondary amino groups, is condensed with a hydrazone of the formula ##STR3## and the resulting azomethine is optionally metallised.

Azomethine pigments of particular interest are those of the formula ##SPC6##

Wherein M denotes a divalent metal atom and A, R and X₁ -X₄ have the meaning indicated, and particularly those of the formula ##SPC7##

Wherein A₁ denotes a benzene, pyridine, pyrimidine or pyrane radical which can also contain a fused benzene nucleus, or denotes a pyrazolone radical, M₁ denotes a copper or nickel atom, X₅ to X₈ have the meaning indicated and R₁ denotes a hydrogen atom or the methyl group.

Azomethine pigments which are particularly preferred are those of the formula ##SPC8##

wherein R₁, M₁ and X₅ to X₈ have the meaning indicated above, Y₃ and Y₄ denote H atoms or halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms, nitro groups or groups of the formula ##STR4## wherein M₂ denotes a Ca, Sr, Ba or Mn atom, and Z represents an O atom or an imino group, and particularly those of the formula ##SPC9##

wherein Z₃ denotes a hydroxyl or methyl group, and R₁, M₁, X₅ to X₈, Y₃ and Y₄ have the meaning indicated above.

Azomethine pigments of particular interest are also those of the formula ##SPC10##

wherein M₁ and X₅ to X₈ have the meaning indicated above, Y₁ denotes a H atom, a carboxyl group, a carbamoyl group, an alkoxycarbonyl or alkylcarbamoyl group containing 2-6 C atoms, a phenylcarbamoyl group which is optionally substituted in the phenyl radical by halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms, or by trifluoromethyl groups, or a group of the formula ##STR5## wherein M₂ has the meaning indicated above, and Y₂ denotes a H atom or halogen atom, an alkoxy group containing 1-4 C atoms, a nitro group or a nitrile group, those of the formula ##SPC11##

wherein R₂ denotes an alkyl group of 1-4 C-atoms, preferably a methyl group, or an optionally substituted aryl group, those of the formula ##SPC12##

wherein R₃ denotes a nitrile or carbamoyl group, those of the formula ##SPC13##

wherein R₄ denotes a nitrile or carbamoyl group, those of the formula ##SPC14##

wherein R₅ denotes a H atom, an alkyl group containing 1-4 C atoms, or an aryl group, or those of the formula ##SPC15##

wherein M₁ and X₅ to X₈ have the meaning indicated above and R₆ denotes an alkyl group containing 1-4 C atoms, an alkoxycarbonyl group containing 2-5 C atoms, a carboxyl group, a carbamoyl group or a group of the formula ##STR6## wherein M₂ denotes a Ca, Sr, Ba or Mn atom, and Y₅ and Y₆ denote H atoms or halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms, nitro, acylamino, carbamoyl or sulphamoyl groups or groups of the formula ##STR7## wherein M₂ denotes a Ca, Sr, Ba or Mn atom.

The isoindolinone hydrazones used as starting materials are obtained by reacting hydrazine with an isoindolinone of the formula ##SPC16##

particularly an isoindolinone of the formula ##SPC17##

X₁ -x₈ and V in the formulae indicated having the indicated meaning.

It is preferable to start from 3-imino-isoindolinone or from 3,3'-dialkoxy-iminoisoindolinones of the formula ##SPC18##

wherein X₅ to X₈ have the meaning indicated and R₃ denotes an alkyl group containing 1-4 C atoms. Those starting materials wherein X₅ to X₈ denote chlorine atoms or hydrogen atoms, are known, and those wherein X₅ and X₇ denote alkoxy, cycloalkoxy, aralkoxy, aryloxy, alkylthio or arylthio groups and X₆ and X₈ denote chlorine atoms, can be obtained by reacting an ammonium salt or ester of tetrachloro-o-cyanobenzoic acid in a hydrophilic organic solvent with a compound of the formula X₅ M₃ wherein X₅ has the meaning indicated above and M₃ denotes an alkali metal atom, and esterifying the product obtained, if necessary.

The following examples of isoindolinones may be mentioned: 3,3-Dimethoxy-4,5,6,7-tetrachloro-isoindolinone, 3,3-dimethoxy-4,5,6,7-tetrabromo-isoindolinone, 3,3,6-trimethoxy-4,5,7-trichloro-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-butoxy-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-phenoxy-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-(p-chlorophenoxy)-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-(o-methylphenoxy)-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-methylmercapto-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-ethylmercapto-isoindolinone, 3,3,4,6-tetramethoxy-5,7-dichloro-isoinodolinone and 3-imino-isoindolinone.

The hydrazones of the isoindolinones mentioned are condensed with compounds of the formula ##STR8## wherein Q denotes an O atom or an imino group, for example a phenylimino group, especially with aldehydes of the formula ##STR9## A and R in the formula indicated having the abovementioned meaning.

Aldehydes or ketones of particular interest are those of the formula ##SPC19##

wherein R₁ denotes a hydrogen atom or the methyl group, and Y₃, Y₄ and Z have the meaning indicated, and especially the hydroxyquinoline aldehydes of the formula ##SPC20##

wherein R₁, Y₃, Y₄ and Z₃ have the meaning indicated.

Aldehydes of particular interest are also those of the following formulae ##SPC21##

wherein R₃ denotes a nitrile or carbamoyl group and R₂ denotes a lower alkyl group or an aryl group, ##SPC22##

wherein R₄ has the same meaning as R₃, ##SPC23##

wherein Y₃ and Y₄ have the meaning indicated above and R₅ denotes a H atom, a lower alkyl group or an aryl group, hydroxynaphthaldehydes of the formula ##SPC24##

wherein Y₁ and Y₂ have the meaning indicated above, or pyrazolone aldehydes of the formula ##SPC25##

wherein R₆, Y₅ and Y₆ have the meaning indicated above. In the above formulae 22 to 29, the aldehyde group can also be replaced by an azomethine group of the formula --CR₁ =Q or --CH=Q wherein Q preferably denotes the phenylimino group.

The following aldehydes or ketones may be mentioned as examples:

1. o-Hydroxybenzaldehydes:

Salicylaldehyde, 4-chloro-2-hydroxybenzaldehyde, 5-chloro-2-hydroxybenzaldehyde, 3-nitro-2-hydroxybenzaldehyde, 5-nitro-2-hydroxybenzaldehyde, 3,5-dichloro-2-hydroxybenzaldehyde, 3,5-dibromo-2-hydroxybenzaldehyde, 5-phenylazo-2-hydroxybenzaldehyde, 5-(2'-chloro-phenylazo)-2-hydroxybenzaldehyde, 5-(2',5'-dichloro-phenylazo)-2-hydroxybenzaldehyde, 5-(2'-methyl-phenylazo)-2-hydroxybenzaldehyde, 5-(2'-methoxy-phenylazo)-2-hydroxybenzaldehyde, 5-(2'-methoxy-4'-nitro-phenylazo)-2-hydroxybenzaldehyde and 5-(2'-methoxy-5'-carbamoyl-phenylazo)-2-hydroxybenzaldehyde.

2. Hydroxynaphthaldehydes:

2-Hydroxynaphthaldehyde, 6-bromo-2-hydroxynaphthaldehyde, 5-nitro-2-hydroxynaphthaldehyde, 2-hydroxy-3-carboxy-naphthaldehyde, 2-hydroxy-3-methoxycarbonyl-naphthaldehyde, 2-hydroxy-3-phenylcarbamoyl-naphthaldehyde, 2-hydroxy-3-(4'-chlorophenylcarbamoyl)-naphthaldehyde, 2-hydroxy-3-(4'-chloro-2'-methylphenylcarbamoyl-naphthaldehyde, 2-hydroxy-3-(2',5'-dimethoxy-3'-chloro-phenyl-carbamoyl-naphthaldehyde, 2-hydroxy-6-bromo-3-carboxynaphthaldehyde and 2-hydroxy-6-bromo-3-phenylcarbamoylnaphthaldehyde.

3. Heterocyclic aldehydes and ketones:

2,6-Dihydroxy-4-methyl-5-cyano-3-pyridine aldehyde, 2,6-dihydroxy-4-methyl-5-carboxy-3-pyridine aldehyde, 2,6-dihydroxy- 4-methyl-5-carbamoyl-3-pyridine aldehyde, 2,4-dihydroxy-3-quinoline aldehyde, 5-chloro-2,4-dihydroxy-3-quinoline aldehyde, 6-chloro-2,4-dihydroxy-3-quinoline aldehyde, 7-chloro-2,4-dihydroxy-3-quinoline aldehyde, 8-chloro-2,4-dihydroxy-3-quinoline aldehyde, 6,8-dichloro-2,4-dihydroxy-3-quinoline aldehyde, 7,8-dichloro-2,4-dihydroxy-3quinoline aldehyde, 6-methyl-2,4-dihydroxy-3-quinoline aldehyde, 7-methyl-2,4-dihydroxy-3-quinoline aldehyde, 8-methyl-2,4-dihydroxy-3-quinoline aldehyde, 6-chloro-8-methyl-2,4-dihydroxy-3-quinoline aldehyde, 2,4-dihydroxy-3-acetyl-quinoline, 2,4-dihydroxy-3-acetyl-6-methylquinoline, 2,4-dihydroxy-3-acetyl-6-chloro-quinoline, 3-hydroxy-4-isoquinolone aldehyde, N-methyl-3-hydroxy-4-isoquinolone aldehyde, N-phenyl-3-hydroxy-4-isoquinolone aldehyde, N-naphthyl-3-hydroxy-4-isoquinolone aldehyde, 2-methyl-4,6-dihydroxy-5-pyrimidine aldehyde, 2-phenyl-4,6-dihydroxy-5-pyrimidine aldehyde, 4-hydroxy-3-quinaldine aldehyde, 6-chloro-4-hydroxy-3-quinaldine aldehyde, 6-methoxy-4-hydroxy-3-quinaldine aldehyde and further aldehydes.

4-Hydroxycoumarin-3-aldehyde, 1-phenyl-3 -methyl-4-formylpyrazolone-5, 1-phenyl-3-carboxy-4-formylpyrazolone-5, 1-phenyl-3-methoxycarbonyl-4-formylpyrazolone-5, 1-phenyl-3-ethoxycarbonyl-4-formylpyrazolone-5, 1-(2'-chlorophenyl)-3-methyl-4-formylpyrazolone-5, 1-(4'-chlorophenyl)-3-methyl-4-formylpyrazolone-5, 1-(2'-methylphenyl)-3-methyl-4-formylpyrazolone-5 and 1-(4'-methylphenyl)-3-methyl-4-formylpyrazolone-5.

Instead of the aldehydes or ketones, it is also possible to use imines, particularly phenylimines, thereof.

For the embodiment (b) of the process according to the invention, the starting materials used are appropriately, on the one hand, isoindolinones of the formula (20), particularly those of the formula (21), and, on the other hand, hydrazones of the aldehydes or ketones of the formulae 22-29).

The condensation of the hydrazone with the oxo compound or the isoindolinone is appropriately carried out in water or an organic solvent, at an elevated temperature, preferably between 50°C and the boiling point of the solvent used. The following examples of solvents may be mentioned: water, alcohol, glacial acetic acid, dioxane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, butyrolactone, glycol monomethyl ether, xylene, chlorobenzene, o-dichlorobenzene, nitrobenzene or mixtures thereof.

As the resulting azomethines are sparingly soluble in the solvents mentioned, they can be isolated easily by filtration. Impurities which may be present can be removed by washing.

For conversion into the metal complexes, the azomethines obtained are treated with agents which donate divalent metals, for example with salts of zinc, manganese, cobalt or iron, but particularly of copper and nickel, or of mixtures of such metals. The formates, acetates or stearates of these metals are preferably used. The metallisation is appropriately carried out in one of the abovementioned solvents.

The metallisation can also be carried out at the same time as the condensation, by condensing the aldehyde together with the hydrazone in one of the abovementioned solvents, in the presence of metal salts.

The metal complexes often additionally contain 0.5-2 mols of water of crystallisation, which, in appropriate instances, exerts a slight influence on the shade of the colorant obtained.

The new colorants represent valuable pigments which can be used, in a finely dispersed form, for pigmenting high molecular organic material, for example cellulose ethers and esters, such as ethylcellulose, nitrocellulose, cellulose acetate or cellulose butyrate, natural resins or synthetic resins, such as polymerisation resins or condensation resins, for example aminoplasts, especially urea-formaldehyde and melamine-formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefines, such as polystyrene, polyvinyl chloride, polyethylene or polypropylene, polyacrylonitrile, polyacrylic acid esters, polyamides, polyurethanes or polyesters, rubber, casein, silicone and silicone resins, individually or as mixtures.

It is immaterial here whether the high molecular compounds mentioned are present as plastic compositions or melts or in the form of spinning solutions, lacquers, paints or printing inks. Depending on the application, it is found to be advantageous to use the new pigments as toners or in the form of preparations.

The resulting colorations are distinguished by good fastness to light and migration.

In the following examples, unless otherwise specified, the parts denote parts by weight, and the percentages denote percentages by weight.

A. Preparation of the complex-forming agents EXAMPLE 1

119.6 g of 3,4,5,6-tetrachloro-2-cyanobenzoic acid methyl ester are dissolved in 600 ml of methanol and 70.6 g of a 30.6% strength methanolic solution of Na methylate. The solution is cooled to 10°C and is added dropwise at 10°C to a solution of 200 ml of hydrazine hydrate in 400 ml of methanol. A yellowish precipitate is formed. The reaction mixture is stirred at room temperature for 2 hours and is then warmed to 35°C over the course of 30 minutes and 200 ml of glacial acetic acid are added at this temperature. After stirring for one hour at room temperature, the product is filtered off and the filter residue is washed with methanol and water. The material filtered off is then extracted by boiling in 1 1 of methylcellosolve for a further 2 hours, filtered off at room temperature and washed with methylcellosolve and methanol. After drying at 70°C, 98 g (82% of theory) of analytically pure 4,5,6,7-tetrachloro-isoindolin-1-on-3-ylidene hydrazine of the formula ##SPC26##

are obtained.

In an analogous manner, 5,7-dichloro-4,6-dimethoxyisoindolin-1-on-3-ylidene hydrazine is obtained in 87% yield from 4,6-dichloro-3,5-dimethoxy-2-cyanobenzoic acid methyl ester, 4,5,7-trichloro-6-methoxy-isoindolin-1-ylidene-3-hydrazine is obtained in 91% yield from 3,5,6-trichloro-4-methoxy-2-cyanobenzoic acid methyl ester and 4,5,7-trichloro-6-phenoxyisoindolin-1-on-3-ylidene hydrazine is obtained in 67% yield from 3,4,6-trichloro-5-phenoxy-2-cyanobenzoic acid methyl ester.

4.49 g of tetrachloro-isoindolin-1-ylidene-3-hydrazine and 4.36 g of 1-formyl-2-hydroxy-3-naphthoic acid anilide in 250 ml of methylcellosolve are heated under reflux for 30 minutes. The thick, yellow precipitate is filtered off at 80°C, washed well with methylcellosolve, alcohol and acetone and dried at 80°C. 8.3 g (97% of theory) of the analytically pure colorant of the formula ##SPC27##

are obtained. Instead of methylcellosolve, Carbitols, dimethylformamide or glacial acetic acid can also be used.

The azomethines of the following formula ##SPC28##

wherein the symbols have the meaning indicated in the following table, are obtained by an analogous process.

                                      Table I                                      __________________________________________________________________________     Example                                                                             X.sub.1                                                                            X.sub.2                                                                           X.sub.3                                                                            X.sub.4                                                                           Y.sub.1      Y.sub.2                                                                           R Shade                                                                              Yield                                 No.                                                                            __________________________________________________________________________     2    Cl  Cl Cl  Cl H            H  H yellow                                                                             94%                                   3    Cl  Cl Cl  Cl COOH         H  H yellow                                                                             78%                                   4    Cl  Cl Cl  Cl                                                                                 ##STR10##   H  H orange                                                                             74%                                   5    Cl  Cl Cl  Cl COOH         Br H yellow                                                                             75%                                   6    CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl COOH         H  H yellow                                                                             87%                                   7    CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl COOH         Br H yellow                                                                             89%                                   8    CH.sub.3 0                                                                         Cl CH.sub.3 O                                                                         Cl H            H  H yellow                                                                             87%                                   9    CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR11##   H  H yellow                                                                             90%                                   __________________________________________________________________________

EXAMPLE 10

5.98 g of 4,5,6,7-tetrachloroisoindolin-1-on-3-ylidene hydrazine and 3.78 g of 2,4-dihydroxy-quinoline-3-aldehyde in glacial acetic acid are boiled under reflux for 5 minutes. The yellow precipitate is filtered off at room temperature, washed well with glacial acetic acid, alcohol and acetone and dried at 80°C. 8.2 g (87% of theory) of the analytically pure pigment of the formula ##SPC29##

are obtained. The hyrazones of the following formula ##SPC30##

wherein the symbols have the meaning indicated in Table II which follows, are obtained by an analogous process.

                                      Table II                                     __________________________________________________________________________     Example                                                                             X.sub.1                                                                            X.sub.2                                                                           X.sub.3                                                                            X.sub.4                                                                           Y.sub.7                                                                           Y.sub.8                                                                            Y.sub.9                                                                           Y.sub.10                                                                           R   Shade                                                                              Yield                                 No.                                                                            __________________________________________________________________________     11   Cl  Cl Cl  Cl H  Cl  H  H   H   yellow                                                                             95%                                   12   Cl  Cl Cl  Cl H  CH.sub.3                                                                           H  H   H   yellow                                                                             92%                                   13   Cl  Cl Cl  Cl H  H   Cl Cl  H   yellow                                                                             90%                                   14   Cl  Cl Cl  Cl Cl H   H  Cl  H   yellow                                                                             67%                                   15   Cl  Cl Cl  Cl H  H   H  H   CH.sub.3                                                                           yellow                                                                             77%                                   16   Cl  Cl OCH.sub.3                                                                          Cl H  H   H  H   H   yellow                                                                             86%                                   17   Cl  Cl OCH.sub.3                                                                          Cl H  Cl  H  H   H   yellow                                                                             91%                                   18   OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H  H   H  H   H   yellow                                                                             78%                                   19   OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H  CH.sub.3                                                                           H  H   H   yellow                                                                             92%                                   20   OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H  Cl  H  H   H   yellow                                                                             85%                                   21   Cl  Cl Cl  Cl H  Cl  H  H   CH.sub.3                                                                           yellow                                                                             81%                                   22   Cl  Cl Cl  Cl H  CH.sub.3                                                                           H  H   CH.sub.3                                                                           yellow                                                                             67%                                   23   OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H  H   H  H   CH.sub.3                                                                           yellow                                                                             91%                                   24   OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H  Cl  H  H   CH.sub.3                                                                           yellow                                                                             82%                                   25   OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H  CH.sub.3                                                                           H  H   CH.sub.3                                                                           yellow                                                                             93%                                   26   OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H  H   H  H   H   yellow                                                                             91%                                   27   Cl  Cl Cl  Cl H  H   Cl Cl  CH.sub.3                                                                           yellow                                                                             82%                                   28   Cl  Cl CH.sub.3 O                                                                         Cl H  H   H  H   CH.sub.3                                                                           yellow                                                                             87%                                   29   CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H  H   Cl Cl  CH.sub.3                                                                           yellow                                                                             97%                                   30   CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H  H   Cl Cl  H   yellow                                                                             91%                                   31   Cl  Cl PhO Cl H  H   H  H   CH.sub.3                                                                           yellow                                                                             87%                                   32   Cl  Cl PhO Cl H  H   H  H   H   yellow                                                                             94%                                   __________________________________________________________________________

EXAMPLE 33

14.50 g of 5,7-dichloro-4,6-dimethoxy-isoindolin-1-on-3-ylidene hydrazine and 13.2 g of 2,4-dihydroxyquinoline-3-N-phenylaldimine in 250 ml of methylcellosolve are boiled under reflux for 1 hour. The yellow precipitate is filtered off at 100°C, washed well with alcohol and dried at 80°C (under vacuum). 18.75 g (82% of theory) of the analytically pure bishydrazine are obtained.

The following hydrazones, for example, are obtained by an analogous process:

                                      Table III                                    __________________________________________________________________________     Example                                                                             X.sub.1                                                                            X.sub.2                                                                           X.sub.3                                                                            X.sub.4                                                                           Y.sub.7                                                                           Y.sub.8                                                                           Y.sub.9                                                                           Y.sub.10                                                                           R   Shade                                                                              Yield                                  No.                                                                            __________________________________________________________________________     34   Cl  Cl Cl  Cl H  Cl H  H   CH.sub.3                                                                           yellow                                                                             72%                                    35   CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H  Cl H  H   CH.sub.3                                                                           yellow                                                                             82%                                    __________________________________________________________________________

EXAMPLE 36

10.95 g of imino-isoindolinone hydrochloride and 12.18 g of the hydrazone of 2,4-dihydroxyquinoline-3-aldehyde are boiled for 5 minutes with 99 g of sodium acetate in 250 ml of glacial acetic acid. The yellow suspension is filtered at 80°C and the precipitate is washed well with glacial acetic acid, alcohol and acetone and dried at 80°C. 16.8 g (84% of theory) of the analytically pure bishydrazone are obtained.

The following bishydrazones, for example, are obtained by an analogous process:

                                      Table IV                                     __________________________________________________________________________     Example                                                                             X.sub.1                                                                           X.sub.2                                                                           X.sub.3                                                                           X.sub.4                                                                           Y.sub.7                                                                           Y.sub.8                                                                           Y.sub.9                                                                           Y.sub.10                                                                           R   Shade                                                                              Yield                                    No.                                                                            __________________________________________________________________________     37   H     H  H  H  H  H  H   CH.sub.3                                                                           yellow                                                                             75%                                      38   H  H  H  H  H  Cl H  H   CH.sub.3                                                                           yellow                                                                             77%                                      __________________________________________________________________________

EXAMPLE 39

5.98 g of 4,5,6,7-tetrachloroisoindolin-1-on-3-ylidene hydrazine and 4.04 g of 1-phenyl-3-methyl-4-formyl-pyrazolone-5 in 200 ml of alcohol are heated under reflux for one hour. The yellow suspension is filtered while warm and the filter residue is washed well with alcohol and dried at 80°C. 9.2 g (95% of theory) of the analytically pure pigment of the formula ##SPC31##

are obtained.

The hydrazones of the following formula ##SPC32##

wherein the symbols have the meaning indicated in Table V which follows, are obtained by an analogous process.

                                      Table V                                      __________________________________________________________________________     Example                                                                             X.sub.1                                                                            X.sub.2                                                                           X.sub.3                                                                            X.sub.4                                                                           X.sub.5                                                                           Y.sub.6                                                                            R.sub.6                                                                              Shade                                                                              Yield                                      No.                                                                            __________________________________________________________________________     40   Cl  Cl Cl  Cl Cl H   CH.sub.3                                                                             yellow                                                                             86%                                        41   OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl Cl H   COOC.sub.2 H.sub.5                                                                   yellow                                                                             68%                                        42   Cl  Cl Cl  Cl H  H   CH.sub.3                                                                             yellow                                                                             100%                                       43   CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H  CH.sub.3                                                                           CH.sub.3                                                                             yellow                                                                             100%                                       44   Cl  Cl Cl  Cl H  CH.sub.3                                                                           CH.sub.3                                                                             yellow                                                                             100%                                       45   CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H  H   CONH.sub.2                                                                           yellow                                                                             73%                                        __________________________________________________________________________

EXAMPLE 46

15.00 g of 4,5,6,7-tetrachloroisoindolin-1-on-3-ylidene hydrazine and 13.25 g of the anil of 4-hydroxycoumarin-3-aldehyde are suspended in 350 ml of methylcellosolve and heated at 100°C for 1 hour. The resulting yellow precipitate is filtered off at room temperature, washed with methylcellosolve, alcohol and acetone and dried at 80°C. 22.3 g (95% of theory) of the colorant of the formula ##SPC33##

are obtained.

EXAMPLE 47

A colorant having similar properties is obtained if 5,7-dichloro-4,6-dimethoxy-isoindolin-1-on-3-ylidene hydrazine is used as the starting material. The yield is 75% of theory.

The bishydrazones described in Examples 1- 30 can also be prepared by a known method from the cyanobenzoic acid esters and the corresponding monohydrazones.

EXAMPLE 48

14.5 g of 5,7-trichloro-4,6-dimethoxy-isoindolin-1-on-3-ylidene hydrazine are suspended in a finely dispersed form in 200 ml of methylcellosolve and heated to 70°C. 11.6 g of 1-phenyl-3-carboxy-4-formyl-pyrazolone-5 in 150 ml of methycellosolve are added slowly to this suspension. The reaction mixture is then kept at 100°C for 2 hours. After cooling to room temperature, the yellow crystals precipitated are filtered off, washed with a little methylcellosolve, with alcohol and acetone and dried at 80°C. 14.7 g (59% of theory) of the analytically pure compound of the formula ##SPC34##

are obtained.

EXAMPLE 49

An analogous compound is obtained in 72% yield, if the instructions of Example 48 are followed, but the starting material is 4,5,6,7-tetrachloro-isoindolin-1-on-3-ylidene hyrazine.

EXAMPLES 50-55

The bishydrazones of the following formula are obtained if the process of Example 10 is followed, using 2-methyl-4-hydroxy-quinoline-3-aldehyde instead of 2,4-dihydroxyquinoline-3-aldehyde. ##SPC35##

The meaning of the symbols is indicated in Table VI which follows.

                  Table VI                                                         ______________________________________                                         Example                                                                               X.sub.1 X.sub.2                                                                               X.sub.3                                                                              X.sub.4                                                                             Y.sub.3                                                                              Shade Yield                             No.                                                                            ______________________________________                                         50     Cl      Cl     Cl    Cl   H     yellow                                                                               97%                               51     CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   H     yellow                                                                               84%                               52     Cl      Cl     Cl    Cl   OCH.sub.3                                                                            yellow                                                                               94%                               53     CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   CH.sub.3 O                                                                           yellow                                                                               89%                               54     Cl      Cl     Cl    Cl   Cl    yellow                                                                               94%                               55     CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   Cl    yellow                                                                               92%                               ______________________________________                                    

EXAMPLES 56-57

The bishydrazones of the formula which follows are obtained analogously if a 4,6-dihydroxyprimidine-5-aldehyde is used instead of 2,4-dihydroxyquinoline-3-aldehyde in the process of Example 10. The meaning of the symbols is given in Table VII. ##SPC36##

                  Table VII                                                        ______________________________________                                         Example                                                                               X.sub.1 X.sub.2                                                                               X.sub.3                                                                              X.sub.4                                                                             R     Shade Yield                             No.                                                                            ______________________________________                                         56     Cl      Cl     Cl    Cl   CH.sub.3                                                                             yellow                                                                               84%                               57     CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   CH.sub.3                                                                             yellow                                                                               81%                               ______________________________________                                    

EXAMPLES 58-63

The bishydrazones of the following formula are obtained analogously if a 4,6-dihydroxypyrimidine-5-N-phenylaldimine is used instead of 2,4-dihydroxyquinoline-3-N-phenylaldimine in the process of Example 33. ##SPC37##

    Example                                                                               X.sub.1 X.sub.2                                                                               X.sub.3                                                                              X.sub.4                                                                             R     Shade Yield                             No.                                                                            ______________________________________                                         58     Cl      Cl     Cl    Cl   H     yellow                                                                               78%                               59     Cl      Cl     CH.sub.3 O                                                                           Cl   H     yellow                                                                               92%                               60     CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   H     yellow                                                                               85%                               61     Cl      Cl     Cl    Cl   CH.sub.3                                                                             yellow                                                                               86%                               62     Cl      Cl     CH.sub.3 O                                                                           Cl   CH.sub.3                                                                             yellow                                                                               85%                               63     CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   CH.sub.3                                                                             yellow                                                                               73%                               ______________________________________                                    

EXAMPLES 64-67

The bishydrazones of the following formula are obtained analogously if a 2,6-dihydroxy-pyridine-5-aldehyde is used instead of 2,4-dihydroxyquinoline-3-aldehyde in the process of Example 10. ##SPC38##

    Example                                                                               X.sub.1 X.sub.2                                                                               X.sub.3                                                                              X.sub.4                                                                             R     Shade Yield                             No.                                                                            ______________________________________                                         64     Cl      Cl     Cl    Cl   CN    yellow                                                                               94%                               65     CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   CN    yellow                                                                               86%                               66     Cl      Cl     Cl    Cl   CONH.sub.2                                                                           yellow                                                                               73%                               67     CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   CONH.sub.2                                                                           yellow                                                                               68%                               ______________________________________                                    

EXAMPLES 68-70

The bishydrazones of the following formula are obtained analogously if a benzimidazolo-6-hydroxypyridine-5-aldehyde is used instead of 2,4-dihydroxyquinoline-3-aldehyde in the process of Example 10 ##SPC39##

    Example                                                                               X.sub.1 X.sub.2                                                                               X.sub.3                                                                              X.sub.4                                                                             R      Shade Yield                            No.                                                                            ______________________________________                                         68     Cl      Cl     Cl    Cl   CN     orange                                                                               92%                              69     CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   CN     yellow                                                                               88%                              70     CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   CONH.sub.2                                                                            yellow                                                                               76%                              ______________________________________                                    

EXAMPLES 71-88

The bishydrazones of the formula which follows are prepared by a known method from the cyanobenzoic acid esters and the corresponding monohydrazones of 3-hydroxy-isoquinolone-4-aldehyde. The meaning of the symbols is given in the table. ##SPC40##

    __________________________________________________________________________     Example                                                                             X.sub.1                                                                            X.sub.2                                                                           X.sub.3                                                                            X.sub.4                                                                           R         Shade                                                                               Yield                                        No.                                                                            __________________________________________________________________________     71   Cl  Cl Cl  Cl H         yellow-                                                                             68%                                                                       orange                                            72   Cl  Cl CH.sub.3 O                                                                         Cl H         orange                                                                              91%                                          73   CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H         yello                                                                               80%                                          74   Cl  Cl Cl  Cl CH.sub.3  orange                                                                              75%                                          75   Cl  Cl CH.sub.3 O                                                                         Cl CH.sub.3  yellow                                                                              90%                                          76   CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl CH.sub.3  yellow                                                                              69%                                          77   Cl  Cl Cl  Cl                                                                                 ##STR12##                                                                               yellow                                                                              87%                                          78   Cl  Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR13##                                                                               yellow                                                                              90%                                          79   CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR14##                                                                               yellow                                                                              65%                                          80   Cl  Cl Cl  Cl                                                                                 ##STR15##                                                                               yellow                                                                              89%                                          81   Cl  Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR16##                                                                               yellow                                                                              90%                                          82   CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR17##                                                                               yellow                                                                              65%                                          83   Cl  Cl Cl  Cl                                                                                 ##STR18##                                                                               yellow                                                                              87%                                          84   Cl  Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR19##                                                                               yellow                                                                              86%                                          85   CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR20##                                                                               yellow                                                                              60% -86                                                                            Cl Cl Cl Cl                                                                     orange194%                              87   Cl  Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR22##                                                                               yellow                                                                              85%                                          88   CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR23##                                                                               orange                                                                              82%                                          __________________________________________________________________________

B. Preparation of the metal complexes EXAMPLE 89

1.72 g of the bishydrazone from Example 1 are reacted, in 70 ml of methylcellosolve, with 0.83 g of Ni(ac)₂.4H₂ O for 4 hours at 90°C. The orange reaction product is filtered off while warm, washed well with methylcellosolve, alcohol and acetone and dried at 80°C. 1.65 g (87%) are obtained of an orange pigment of the formula ##SPC41##

which colours PVC in orange shades of good fastness to light and migration. The metallisation can also be carried out, for example, in dimethylformamide or Carbitol. The following metal complexes are prepared by an analogous process: ##SPC42##

                                      Table VIII                                   __________________________________________________________________________     Example                                                                             X.sub.1                                                                            X.sub.2                                                                           X.sub.3                                                                            X.sub.4                                                                           Y.sub.1     Y.sub.2                                                                           M Shade                                      No.                                                                            __________________________________________________________________________     90   Cl  Cl Cl  Cl H           H  Cu                                                                               orange                                     91   Cl  Cl Cl  Cl H           H  Zn                                                                               orange                                     92   CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H           H  Ni                                                                               orange                                     93   CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H           H  Cu                                                                               brown                                      94   Cl  Cl Cl  Cl COOH        H  Ni                                                                               orange                                     95   Cl  Cl Cl  Cl COOH        H  Zn                                                                               orange                                     96   Cl  Cl Cl  Cl COOH        H  Cd                                                                               yellow                                     97   CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl COOH        H  Ni                                                                               orange                                     98   CH.sub.3 0                                                                         Cl CH.sub.3 O                                                                         Cl COOH        H  Cu                                                                               yellow                                     99   Cl  Cl Cl  Cl COOH        Br Ni                                                                               orange                                     100  Cl  Cl Cl  Cl COOH        Br Cu                                                                               yellow                                     101  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl COOH        Br Ni                                                                               yellow-                                                                        orange                                     102  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl COOH        Br Cu                                                                               yellow                                     103  Cl  Cl Cl  Cl                                                                                 ##STR24##  H  Cu                                                                               brown                                      104  Cl  Cl Cl  Cl                                                                                 ##STR25##  H  Zn                                                                               orange                                     105  Cl  Cl Cl  Cl                                                                                 ##STR26##  H  Cu                                                                               brown                                      106  Cl  Cl Cl  Cl                                                                                 ##STR27##  H  Zn                                                                               orange                                     107  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR28##  H  Ni                                                                               brown                                      108  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR29##  H  Cu                                                                               brown                                      109  H   H  H   H  H           H  Ni                                                                               yellow                                     110  H   H  H   H  H           H  Cu                                                                               yellow                                     111  H   H  H   H  H           H  Co                                                                               yellow-                                                                        brown                                      __________________________________________________________________________

EXAMPLE 112

1.48 g of the bishydrazone of Example 20 are reacted in 60 ml of methylcellosolve with 0.66 g of Cu(ac)₂.H₂ O for 3 hours at 90°C. The green-yellow reaction product is filtered off while warm, washed well with methylcellosolve, alcohol and acetone and dried at 100°C. 1.55 g (93%) are obtained of a greenish-tinged yellow pigment of the formula ##SPC43##

which colours PVC in greenish-tinged yellow shades of outstanding fastness to light and migration.

The metal complexes of the formula ##SPC44##

wherein the symbols have the meaning indicated in Table IX which follows are obtained by an analogous process.

                                      Table IX                                     __________________________________________________________________________     Example                                                                             X.sub.1                                                                            X.sub.2                                                                           X.sub.3                                                                            X.sub.4                                                                           Y.sub.7                                                                           Y.sub.8                                                                            Y.sub.9                                                                           Y.sub.10                                                                           R   M Shade                                   No.                                                                            __________________________________________________________________________     113  Cl  Cl Cl  Cl H  H   H  H   H   Ni                                                                               yellow                                  114  Cl  Cl Cl  Cl H  H   H  H   H   Cu                                                                               yellow-green                            115  Cl  Cl Cl  Cl H  H   H  H   H   Zn                                                                               yellow                                  116  Cl  Cl Cl  Cl H  Cl  H  H   H   Ni                                                                               yellow                                  117  Cl  Cl Cl  Cl H  Cl  H  H   H   Cu                                                                               yellow-green                            118  Cl  Cl Cl  Cl H  Cl  H  H   H   Zn                                                                               yellow                                  119  Cl  Cl Cl  Cl H  CH.sub.3                                                                           H  H   H   Ni                                                                               yellow-orange                           120  Cl  Cl Cl  Cl H  CH.sub.3                                                                           H  H   H   Cu                                                                               yellow                                  121  Cl  Cl Cl  Cl H  CH.sub.3                                                                           H  H   H   Zn                                                                               yellow                                  122  Cl  Cl Cl  Cl H  H   H  Cl  H   Ni                                                                               yellow                                  123  Cl  Cl Cl  Cl H  H   H  Cl  H   Cu                                                                               yellow-green                            124  Cl  Cl Cl  Cl H  H   H  Cl  H   Zn                                                                               yellow                                  125  Cl  Cl Cl  Cl H  H   Cl Cl  H   Ni                                                                               yellow                                  126  Cl  Cl Cl  Cl H  H   Cl Cl  H   Cu                                                                               yellow-green                            127  Cl  Cl Cl  Cl H  H   Cl Cl  H   Zn                                                                               yellow                                  128  Cl  Cl OCH.sub.3                                                                          Cl H  H   H  H   H   Ni                                                                               yellow                                  129  Cl  Cl OCH.sub.3                                                                          Cl H  H   H  H   H   Cu                                                                               green-yellow                            130  Cl  Cl OCH.sub.3                                                                          Cl H  Cl  H  H   H   Ni                                                                               yellow                                  131  Cl  Cl OCH.sub.3                                                                          Cl H  Cl  H  H   H   Cu                                                                               yellow-green                            132  OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H  H   H  H   H   Ni                                                                               yellow                                  133  OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H  H   H  H   H   Cu                                                                               yellow                                  134  OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H  CH.sub.3                                                                           H  H   H   Ni                                                                               yellow                                                                         greenish-                               135  OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H  CH.sub.3                                                                           H  H   H   Cu                                                                               tinged yellow                           136  OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H  Cl  H  H   H   Ni                                                                               yellow                                  137  Cl  Cl Cl  Cl H  H   H  H   CH.sub.3                                                                           Ni                                                                               yellow                                  138  Cl  Cl Cl  Cl H  H   H  H   CH.sub.3                                                                           Cu                                                                               yellow                                  139  Cl  Cl Cl  Cl H  CH.sub.3                                                                           H  H   CH.sub.3                                                                           Ni                                                                               yellow                                  140  Cl  Cl Cl  Cl H  CH.sub.3                                                                           H  H   CH.sub.3                                                                           Cu                                                                               yellow                                  141  Cl  Cl Cl  Cl H  Cl  H  H   CH.sub.3                                                                           Ni                                                                               yellow-brown                            142  Cl  Cl Cl  Cl H  Cl  H  H   CH.sub.3                                                                           Cu                                                                               yellow-brown                            143  OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H  H   H  H   CH.sub.3                                                                           Ni                                                                               yellow                                  144  OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H  H   H  H   CH.sub.3                                                                           Cu                                                                               yellow                                  145  OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H  CH.sub.3                                                                           H  H   CH.sub.3                                                                           Ni                                                                               yellow                                  146  OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H  CH.sub.3                                                                           H  H   CH.sub.3                                                                           Cu                                                                               yellow                                  147  OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H  Cl  H  H   CH.sub.3                                                                           Ni                                                                               yellow                                  148  OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H  Cl  H  H   CH.sub.3                                                                           Cu                                                                               yellow                                  149  OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H  Cl  H  H   CH.sub.3                                                                           Co                                                                               yellow-brown                                                                   greenish-                               150  H   H  H   H  H  H   H  H   H   Ni                                                                               tinged yellow                                                                  greenish-                               151  H   H  H   H  H  H   H  H   H   Cu                                                                               tinged yellow                           152  CH.sub.3 O                                                                         Cl OCH.sub.3                                                                          Cl H  H   Cl Cl  H   Ni                                                                               yellow                                                                         greenish-                               153  CH.sub.3 O                                                                         Cl OCH.sub.3                                                                          Cl H  H   Cl Cl  H   Cu                                                                               tinged yellow                           154  H   H  H   H  H  H   H  H   CH.sub.3                                                                           N yellow                                  155  H   H  H   H  H  H   H  H   CH.sub.3                                                                           Cu                                                                               yellow-green                            156  H   H  H   H  H  Cl  H  H   CH.sub.3                                                                           N yellow                                  157  H   H  H   H  H  Cl  H  H   CH.sub.3                                                                           Cu                                                                               yellow-green                            158  Cl  Cl Cl  Cl H  H   Cl Cl  CH.sub.3                                                                           Ni                                                                               orange                                  159  Cl  Cl Cl  Cl H  H   Cl Cl  CH.sub.3                                                                           Cu                                                                               yellow                                  160  Cl  Cl CH.sub.3 O                                                                         Cl H  H   H  H   CH.sub.3                                                                           Ni                                                                               yellow                                  161  Cl  Cl CH.sub.3 O                                                                         Cl H  H   H  H   CH.sub.3                                                                           Cu                                                                               yellow                                  162  Cl  Cl PhO Cl H  H   H  H   H   Ni                                                                               yellow                                  163  Cl  Cl PhO Cl H  H   H  H   H   Cu                                                                               yellow-green                            164  Cl  Cl PhO Cl H  H   H  H   CH.sub.3                                                                           Ni                                                                               yellow                                  165  Cl  Cl PhO Cl H  H   H  H   CH.sub.3                                                                           Cu                                                                               yellow                                  166  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H  Cl  H  H   CH.sub.3                                                                           Ni                                                                               yellow                                  167  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H  Cl  H  H   CH.sub.3                                                                           Cu                                                                               yellow-green                            168  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H  H   Cl Cl  H   Ni                                                                               yellow                                  169  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H  H   Cl Cl  H   Cu                                                                               yellow-green                            170  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H  H   Cl Cl  CH.sub.3                                                                           Ni                                                                               yellow                                  171  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H  H   Cl Cl  CH.sub.3                                                                           Cu                                                                               yellow                                  __________________________________________________________________________

EXAMPLE 172

2.40 g of the bishydrazone of Example 40 are reacted in 60 ml of methylcellosolve with 1.10 g of Cu(ac)₂.H₂ O for 5 hours at 90°C. The reaction product is filtered off, washed with methylcellosolve and alcohol and dried at 80°C. 2.30 g (85% of theory) are obtained of a yellow-brown pigment of the formula ##SPC45##

which colours PVC in yellow shades of good fastness to light and migration.

The metal complexes of the formula ##SPC46##

wherein the symbols have the meaning indicated in Table X which follows, are obtained by an analogous process.

                                      Table X                                      __________________________________________________________________________     Example                                                                             X.sub.1                                                                            X.sub.2                                                                           X.sub.3                                                                            X.sub.4                                                                           Y.sub.5                                                                           Y.sub.6                                                                            R.sub.6                                                                              M Shade                                        No.                                                                            __________________________________________________________________________     173  Cl  Cl Cl  Cl H      CH.sub.3                                                                             Ni                                                                               yellow                                       174  Cl  Cl Cl  Cl H      CH.sub.3                                                                             Zn                                                                               yellow                                       175  Cl  Cl Cl  Cl Cl     CH.sub.3                                                                             Ni                                                                               yellow                                       176  Cl  Cl Cl  Cl Cl     CH.sub.3                                                                             Cu                                                                               yellow-green                                 177  OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H      COOC.sub.2 H.sub.5                                                                   Ni                                                                               yellow                                       178  OCH.sub.3                                                                          Cl OCH.sub.3                                                                          Cl H      COOC.sub.2 H.sub.5                                                                   Cu                                                                               yellow-brown                                 179  Cl  Cl Cl  Cl H  CH.sub.3                                                                           CH.sub.3                                                                             Ni                                                                               yellow                                       180  Cl  Cl Cl  Cl H  CH.sub.3                                                                           CH.sub.3                                                                             Cu                                                                               yellow                                       181  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H  CH.sub.3                                                                           CH.sub.3                                                                             Ni                                                                               yellow                                       182  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H  CH.sub.3                                                                           CH.sub.3                                                                             Cu                                                                               yellow-green                                 183  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H  H   CONH.sub.2                                                                           Ni                                                                               yellow                                       184  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H  H   CONH.sub.2                                                                           Cu                                                                               yellow-green                                 __________________________________________________________________________

EXAMPLES 185-188

The metal complexes of the following formula ##SPC47##

wherein the symbols have the meaning indicated in Table XI which follows, are obtained by the methods described above from the bishydrazones of Examples 46 and 47.

                  Table XI                                                         ______________________________________                                         Example                                                                               X.sub.1 X.sub.2                                                                               X.sub.3                                                                              X.sub.4                                                                             M    Shade                                    No.                                                                            ______________________________________                                         185    Cl      Cl     Cl    Cl   Ni   yellow                                   186    Cl      Cl     Cl    Cl   Cu   yellow-green                             187    OCH.sub.3                                                                              Cl     OCH.sub.3                                                                            Cl   Ni   yellow                                   188    OCH.sub.3                                                                              Cl     OCH.sub.3                                                                            Cl   Cu   yellow-green                             ______________________________________                                    

EXAMPLES 189-197

The metal complexes of the following formula are obtained by reacting the bishydrazones obtained in accordance with Example 1 with the corresponding metal salts ##SPC48##

The following table indicates the meaning of the symbols:

                  Table XII                                                        ______________________________________                                         Example  Y.sub.1  Y.sub.2                                                                               Y.sub.3                                                                             Y.sub.4                                                                             M   Shade                                   No.                                                                            ______________________________________                                         189      H        H      H    H    Ni  yellow                                  190      H        H      H    H    Zn  yellow                                  191      H        H      H    H    Cd  yellow                                  192      OC.sub.2 H.sub.5                                                                        H      H    H    Ni  orange                                  193      OC.sub.2 H.sub.5                                                                        H      H    H    Zn  yellow                                  194      OC.sub.2 H.sub.5                                                                        H      H    H    Cd  yellow                                  195      Cl       H      Cl   H    Ni  brown                                   196      Cl       H      Cl   H    Zn  yellow                                  197      Cl       H      Cl   H    Cd  yellow                                  ______________________________________                                    

EXAMPLE 198

1.50 g of the bishydrazone of Example 48 are heated in 70 ml of methylcellosolve with 0.63 g of Cu(ac)₂.H₂ O for 3 hours at 100°C. The yellow-green suspension is filtered hot; the filter residue is washed well with methylcellosolve, alcohol and acetone and dried at 80°C. 1.2 g (70% of theory) are obtained of a greenish-tinged yellow pigment of the formula ##SPC49##

EXAMPLE 199

The procedure is as indicated in Example 198, but the bishydrazone of Example 49 is used as the starting material. The greenish-tinged yellow pigment of the formula ##SPC50##

is obtained.

EXAMPLE 200 Ba salt of the colorant according to Example 198

1.50 g of the bishydrazone of Example 48 are reacted in 70 ml of methylcellosolve with 0.63 g of Cu(ac)₂.H₂ O for 3 hours at 100°C. A solution of 1 g of Ba(OH)₂.8H₂ O in 20 ml of water is run dropwise into this yellow-green suspension. The reaction mixture is heated for a further 2 hours at 100°C and is then filtered hot. The filter residue is washed well with methylcellosolve, water, alcohol and acetone and dried at 90°C. 1.8 g are obtained of a yellow-green pigment which colours PVC in greenish-tinged yellow shades of good fastness to light and migration.

EXAMPLE 201

The barium salt of the copper complex of Example 199 is prepared by the process of Example 200. A pigment is obtained which colours PVC in greenish-tinged yellow shades of good fastness to light and migration.

EXAMPLE 202

The nickel complex of the same colorant is prepared by the process of Example 200. It colours PVC in yellow shades of good fastness to light and migration.

EXAMPLES 203-206

The metal complexes of the following formula are obtained by reacting the bishydrazones obtained in accordance with Examples 56 and 57, with the corresponding metal salts. ##SPC51##

The following table indicates the meaning of the symbols.

                  Table XIII                                                       ______________________________________                                         Example X.sub.1 X.sub.2                                                                               X.sub.3                                                                              X.sub.4                                                                             M   Shade                                    No.                                                                            ______________________________________                                         203     Cl      Cl     Cl    Cl   Ni  yellow                                   204     Cl      Cl     Cl    Cl   Cu  yellow-green                             205     CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   Ni  yellow                                   206     CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   Cu  yellow-green                             ______________________________________                                    

EXAMPLES 207-218

The metal complexes of the following formula are obtained by reacting the bishydrazones of Examples 58-63 with the corresponding metal salts. ##SPC52##

                  Table XIV                                                        ______________________________________                                         Example                                                                               X.sub.1 X.sub.2                                                                               X.sub.3                                                                              X.sub.4                                                                             R     M   Shade                               No.                                                                            ______________________________________                                         207    Cl      Cl     Cl    Cl   H     Ni  yellow                              208    Cl      Cl     Cl    Cl   H     Cu  yellow-                                                                        green                               209    Cl      Cl     CH.sub.3 O                                                                           Cl   H     Ni  yellow                              210    Cl      Cl     CH.sub.3 O                                                                           Cl   H     Cu  yellow-                                                                        green                               211    CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   H     Ni  yellow                              212    CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   H     Cu  yellow-                                                                        green                               213    Cl      Cl     Cl    Cl   CH.sub.3                                                                             Ni  yellow                              214    Cl      Cl     Cl    Cl   CH.sub.3                                                                             Cu  yellow-                                                                        green                               215    Cl      Cl     CH.sub.3 O                                                                           Cl   CH.sub.3                                                                             Ni  yellow                              216    Cl      Cl     CH.sub.3 O                                                                           Cl   CH.sub.3                                                                             Cu  yellow-                                                                        green                               217    CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   CH.sub.3                                                                             Ni  yellow                              218    CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   CH.sub.3                                                                             Cu  yellow-                                                                        green                               ______________________________________                                    

EXAMPLES 219-230

The metal complexes of the following formula are obtained by reacting the bishydrazones obtained in accordance with Examples 50-55 with the corresponding metal salts. ##SPC53##

The following table indicates the meaning of the symbols.

                  Table XV                                                         ______________________________________                                         Example                                                                               X.sub.1 X.sub.2                                                                               X.sub.3                                                                              X.sub.4                                                                             Y.sub.3                                                                              M   Shade                               No.                                                                            ______________________________________                                         219    Cl      Cl     Cl    Cl   H     Ni  yellow                              220    Cl      Cl     Cl    Cl   H     Cu  yellow-                                                                        green                               221    CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   H     Ni  yellow                              222    CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   H     Cu  yellow-                                                                        green                               223    Cl      Cl     Cl    Cl   CH.sub.3 O                                                                           Ni  yellow                              224    Cl      Cl     Cl    Cl   CH.sub.3 O                                                                           Cu  yellow-                                                                        green                               225    CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   CH.sub.3 O                                                                           Ni  yellow                              226    CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   CH.sub.3 O                                                                           Cu  yellow-                                                                        green                               227    Cl      Cl     Cl    Cl   Cl    Ni  yellow                              228    Cl      Cl     Cl    Cl   Cl    Cu  yellow-                                                                        green                               229    CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   Cl    Ni  yellow                              230    CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   Cl    Cu  yellow-                                                                        green                               ______________________________________                                    

EXAMPLES 231-238

The metal complexes of the following formula are obtained by reacting the bishydrazones of Examples 64-67 with the corresponding metal salts. ##SPC54##

    Example                                                                               X.sub.1 X.sub.2                                                                               X.sub.3                                                                              X.sub.4                                                                             R      M   Shade                              No.                                                                            ______________________________________                                         231    Cl      Cl     Cl    Cl   CN     Ni  yellow                             232    Cl      Cl     Cl    Cl   CN     Cu  yellow                             233    CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   CN     Ni  yellow                             234    CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   CN     Cu  green-                                                                         yellow                             235    Cl      Cl     Cl    Cl   CONH.sub.2                                                                            Ni  yellow                             236    Cl      Cl     Cl    Cl   CONH.sub.2                                                                            Cu  yellow                             237    CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   CONH.sub.2                                                                            Ni  yellow                             238    CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   CONH.sub.2                                                                            Cu  yellow-                                                                        green                              ______________________________________                                    

EXAMPLES 239-245

The metal complexes of the following formula are obtained by reacting the bishydrazones of Examples 68-70 with the corresponding metal salts. ##SPC55##

    Example                                                                               X.sub.1 X.sub.2                                                                               X.sub.3                                                                              X.sub.4                                                                             R      M   Shade                              No.                                                                            ______________________________________                                         239    Cl      Cl     Cl    Cl   CN     Ni  orange                             240    Cl      Cl     Cl    Cl   CN     Cu  yellow                             241    CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   CN     Ni  yellow                             242    CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   CN     Cu  yellow-                                                                        green                              243    CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   CN     Co  yellow                             244    CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   CONH.sub.2                                                                            Ni  yellow                             245    CH.sub.3 O                                                                             Cl     CH.sub.3 O                                                                           Cl   CONH.sub.2                                                                            Cu  brown                              ______________________________________                                    

EXAMPLES 246-277

The metal complexes of the following formula are obtained by reacting the bishydrazones of the Examples under 1 with the corresponding metal salts. ##SPC56##

    __________________________________________________________________________     Example                                                                             X.sub.1                                                                            X.sub.2                                                                           X.sub.3                                                                            X.sub.4                                                                           R         M  Shade                                          No.                                                                            __________________________________________________________________________     246  Cl  Cl Cl  Cl H         Ni red-brown                                      247  Cl  Cl Cl  Cl H         Cu brown                                          248  Cl  Cl CH.sub.3 O                                                                         Cl H         Ni red-brown                                      249  Cl  Cl CH.sub.3 O                                                                         Cl H         Cu yellow-brown                                   250  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H         Ni yellow-brown                                   251  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl H         Cu yellow                                         252  Cl  Cl Cl  Cl CH.sub.3  Ni red-brown                                      253  Cl  Cl Cl  Cl CH.sub.3  Cu brown                                          254  Cl  Cl CH.sub.3 O                                                                         Cl CH.sub.3  Ni red-brown                                      255  Cl  Cl CH.sub.3 O                                                                         Cl CH.sub.3  Cu brown                                          256  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl CH.sub.3  Ni red-brown                                      257  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl CH.sub.3  Cu yellow-brown                                   258  Cl  Cl Cl  Cl                                                                                 ##STR30##                                                                               Ni red                                            259  Cl  Cl Cl  Cl                                                                                 ##STR31##                                                                               Cu orange                                         260  Cl  Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR32##                                                                               Ni red                                            261  Cl  Cl CH.sub. 3 O                                                                        Cl                                                                                 ##STR33##                                                                               Cu orange                                         262  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR34##                                                                               Ni red-brown                                      263  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR35##                                                                               Cu yellow-brown                                   264  Cl  Cl Cl  Cl                                                                                 ##STR36##                                                                               Ni red                                            265  Cl  Cl Cl  Cl                                                                                 ##STR37##                                                                               Cu yellow-orange                                  266  Cl  Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR38##                                                                               Ni red-brown                                      267  Cl  Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR39##                                                                               Cu yellow-brown                                   268  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR40##                                                                               Ni red-brown                                      269  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR41##                                                                               Cu yellow-brown                                   270  Cl  Cl Cl  Cl                                                                                 ##STR42##                                                                               Ni red                                            271  Cl  Cl Cl  Cl                                                                                 ##STR43##                                                                               Cu red-brown                                      272  Cl  Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR44##                                                                               Ni red-brown                                      273  Cl  Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR45##                                                                               Cu yellow-brown                                   274  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR46##                                                                               Ni red-brown                                      275  CH.sub.3 O                                                                         Cl CH.sub.3 O                                                                         Cl                                                                                 ##STR47##                                                                               Cu yellow-brown                                   276  Cl  Cl Cl  Cl                                                                                 ##STR48##                                                                               Ni red                                            277  Cl  Cl Cl  Cl                                                                                 ##STR49##                                                                               Cu red-brown                                      __________________________________________________________________________

EXAMPLE 278

All the metal complexes described can also be prepared directly from the components, isoindolinone-3-ylidene hydrazine, hydroxy-aldehyde or hydroxy-ketone and metal salt by the one-pot method.

1.45 g of 5,7-dichloro-4,6-dimethoxy-isoindolin-1-on-3-ylidene hydrazine, 0.945 g of 2,4-dihydroxyquinoline-3-aldehyde and 1.25 g of Ni(ac)₂.4H₂ O are reacted for 1 hour at 100°C in 50 ml of glacial acetic acid. The yellow-orange suspension is filtered at 80°C, washed well with glacial acetic acid, alcohol and acetone and dried at 80°C. 2.40 g (93% of theory) of a yellow pigment, identical with the product of Example 132, are obtained.

The formation of the metal complex can also be carried out in, for example, dimethylformamide, methylcellosolve, ethylcellosolve, Carbitol and glycol, instead of glacial acetic acid.

EXAMPLE 279

65 parts of stabilised polyvinyl chloride, 35 parts of dioctyl phthalate and 0.2 part of the colorant obtained in accordance with Example 89 are stirred together with one another and are then worked for 7 minutes at 140°C on a twin-roll calender. An orange sheet of very good fastness to light and migration is obtained.

EXAMPLE 280

1.00 g of the pigment prepated according to Example 113 is finely ground on an Engelsmann grinding machine together with 4.00 g of printer's varnish of the following composition:

29.4% of linseed oil-stand oil (300 poises),

67.2% of linseed oil-stand oil (20 poises),

2.1% of cobalt octoate (8% of Co) and

1.3% of lead octoate (24% of Pb)

and is then printed on art printing paper at 1 g/m² in the letterpress process with the aid of a block. A strong, pure shade of yellow, having good transparency and good gloss, is obtained. Very brilliant green shades can be produced in three- or four-colour printing by overprinting on blue.

The pigment is also suitable for other printing processes, such as gravure printing, offset printing and flexographic printing, and here too gives very good results. 

What we claim is:
 1. An azomethine pigment of the formula ##SPC57##wherein M is, copper or nickel; R is hydrogen, or alkyl of 1-6 carbon atoms; X₆ and X₈ is hydrogen, halogen, or nitro; X₅ and X₇ is hydrogen, halogen, alkoxy of 1-6 carbon atoms, alkyl mercapto of 1-6 carbon atoms, cycloalkoxy containing 5-6 carbon atoms, phenoxy, chloro phenoxy, methyl phenoxy, or nitro; and R₂ is lower alkyl, phenyl, or phenyl substituted by methyl.
 2. An azomethine pigment according to claim 1 of the formula ##SPC58## 